Preparation of benzothieno[2,3-f]-1,4-oxazepin- and -thiazepin-5(2H)-ones and of benzothieno[3,2-e]-1,4-diazepin-5-ones
Preparation of benzothieno[2,3-f]-1,4-oxazepin- and -thiazepin-5(2H)-ones and of benzothieno[3,2-e]-1,4-diazepin-5-ones
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DOI：
10.1021/jo960235m
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发表时间：
1996-08-23
影响因子：
3.6
通讯作者：
Stoss, P
中科院分区：
文献类型：
--
作者：
Khatana, SS;Boschelli, DH;Stoss, P
抗肿瘤剂PD 144795，1a，减少活化内皮细胞表面粘附分子的表达。结构A的其它苯并[B]噻吩-2-甲酰胺，包括1 B、1 c和1 d，也具有这种性质。我们感兴趣的是制备新的三环衍生物A，即B，含有一个七元环。3在高压下用阮内钴和氢处理容易获得的24直接产生氧氮杂卓3（方案1）。由于在这些条件下发生醚裂解，也获得了不同量的4。用包括10%铑和2%Pd/C的其它氢化催化剂还原2仅得到4。化合物6通过55与氯乙腈在叔丁醇钾存在下反应制备。在通过阮内钴方法将6环化为8的尝试失败后，我们采用了两步方案。用硼烷-甲基硫醚将6的腈基还原成相应的胺7，其在用甲醇钠处理后提供
The antiinflammatory agent PD 144795, 1a, reduces the expression of adhesion molecules on the surface of activated endothelial cells. 1, 2 This property is shared by additional benzo [b] thiophene-2-carboxamides of structure A, including 1b, 1c, and 1d. We were interested in preparing the novel tricyclic derivatives of A, namely B, that contain a seven-membered ring. 3Treatment of readily available 24 with Raney cobalt and hydrogen under elevated pressure yielded the oxazepine 3 directly (Scheme 1). Due to ether cleavage occurring under these conditions varying amounts of 4 were also obtained. Reduction of 2 with other hydrogenation catalysts including 10% rhodium and 2% Pd/C gave exclusively 4. Compound 6 was prepared by reaction of 55 with chloroacetonitrile in the presence of potassium tert-butoxide. After unsuccessful attempts to cyclize 6 to 8 by the Raney cobalt method, we employed a twostep protocol. The nitrile group of 6 was reduced with borane-methyl sulfide to the corresponding amine 7, which upon treatment with sodium methoxide provided